tannery 2007 final
TRANSCRIPT
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The Federal
Environmental Protection Authority
Environmental impact Assessment Guideline forTanneries
NOT FOR CITATION
This guidelines is still under development and shall be binding afterconsensus is reached between the Environmental ProtectionAuthority and the Environmental Units of Competent SectoralAgencies
April 2005Addis Ababa
Ethiopia
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Acronyms
AOX-Adsorbable Orgainc Halogen
APE-Alkyl Phenol Ethoxylates
EDDS Ethylene-diamine-Di-Succinate
EDTA- Ethylene-Diamine Tetra-Acetate
EIA- Environnemental Impact Assessment
EPA-Environmental Protection Authority
EPE-Environmental Policy of Ethiopia
FAO-Food Agricultural Organization
GDP- Gross Domestic Product
HVLP-High Volume Low Pressure
ISO- International Standards Organization
MGDA-Methyl-Glycine-Di-Acetate
NPE-Nonytphenolethoxylaties
NTA-Nitrilo-Tri-Acetate
BAT-Best Available Techniques
EU-European Union
EA-Environmental Assessment
ETP-Effluent Treatment Plant
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Glossary
Aerobic : process involving areas of oxygen.
Anaerobic : process without oxygen.
Asphyxia: is the eventual result of prolonged exposure to an atmosphere containing too little oxygen tosustain life; many such situations involve the displacement of oxygen-containing air with an asphyxiant
gas.
Assimilative capacity: is the capacity of the natural environment to absorb waste materials without
being affected.
Bating : is the manufacturing step which follows liming and precedes pickling. The purpose of bating is to
declime the hides, reduce swelling, peptize fibres, and remove protein degradation products.
Beam house : is that portion of the tannery where the hides are washed, limed, fleshed and unhaired,
when necessary, prior to the tanning process.
Biochemical Oxygen Demand (BOD) : is a measure of the quantity of oxygen which may be consumed
while biologically degrading the organic constituents. The test is carried out over five days and the result
expressed as BOD 5.
Chemical Oxygen Demand (COD) : is a measure of the quantity of oxygen consumed during chemical
oxidation of the constituents of an effluent with potassium dichromate.
Deliming : is the process which removes the lime from hides coming from the beamhouse.
Disposal : is the act of discharging a waste or effluent into the environment.
Environmental standard : is a legal level of a pollutant set by regulation.
Eutrophication : is the nutrient enrichment of natural waterbodies leading to excessive growth of algae
and weeds so as to ultimately choke the normal aquatic life processes.
Finishing : is the final set of processing steps performed on a tanned hide. These operations follow the
retain-colour-fatliquor processes, and include the many dry processes involved in converting the hide into
the final tannery product.
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Full chrome: is used to refer to a tannery process. "Full" is sometimes added to the term "chrome
tanned" to emphasize that the leather has not been tanned by the semi-chrome or combination chrome
processes.
Grain : can mean:
a) the outer, or hair side, of a hide or skin that has been split into layers; or
b) the pattern visible on the outer surface of a hide or skin after the hair or wool has been removed.
Leather : is a general term for hide or skin which still retains its original fibrous structure more or less
intact, and which has been treated so as to be non-putrescible even after treatment with water.
Pickling : is the process that follows bating, whereby the skin or hide is immersed in a brine and acid
solution to bring it to an acid condition. It prevents precipitation of chromium salts on the hide.
Pollution : is a state that occurs when assimilative capacity of the environment is exceeded, resulting in
illness or death of organisms, and undesirable ecological changes.
Retaining : is the process of subjecting a skin, which has been first more or less completely tanned by
one process or one kind or blend of tanning materials, to a second tanning process involving similar or,
more usually, different tanning materials.
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1 Introduction and Background
1.1. The Ethiopian economy is dominated by agriculture, which accounts for about 50% of the total,and 90% of the export and 85% of the total employment. Similarly, the industrial sector isbasically dominated by agro industries that contribute about 12% to the GDP. This sectorsupplies important consumers goods both to domestic and external markets.
1.2 Leather and leather products are among the main manufacturing export products. Within themanufacturing sectors, the leather industry comes as the leading exporter and accounting for upto 67% of the total manufactured exports. The leather industry is one of the many economicsectors, which the government has given due consideration for the development. The countrywas able to generate above US$60million.in the year 2004 from its leather industry.
1.3. Ethiopia possesses 12, 15 and 22 percent of the world cattle, sheep and goats populationrespectively. This showed that, the country is one of the most promising leather producingcountry in Africa. The report issued by the Ministry of Agriculture and Rural Developmentindicated that from its cattle resources Ethiopia is able to produce about 2.4 million of hides 8.3million ship skins, 7 million goat skins annually.
1.4 Currently there are 20 tanneries, which are operational in this sector employing about 6000workers. The current production capacity based on 15 tanneries is estimated at 6,000,000 to8,000 000 kilograms of hides and 20, 000, 000 to 25,000,000 skins. The hides are processed upto wet blues, crust and finished leather. The wet blues and crust hides are produced for exportand the remaining low quality are finished for local market in the form of garments uppers andlinings.
1.5. However, the industrial establishments huge potential of for sustained economic development ofthe country has been constrained for they were not designed and operated in sustainablemanner for some time now. In Ethiopia, the annual volume of liquid waste discharge from the 15tanneries based on their annual production capacities is estimated to vary between 2,000,000and 2,500,000 cubic meters.
The major features of Ethiopian Industries thus include among other things that, they:o are based on obsolete technologies;o were operating in the absence of appropriate environmental laws and standards as well
as low level of environmental awareness,o did not subject to impact assessment process;o are not located in well defined industrial zones and concentrated in urban centres along
multipurpose rivers and streams;o Most of tanneries do not have treatment facilities and environmental management
systems, as a result simply discharging their wastes into the environment; etc.
1.6. Thus, are causing serious environmental and public health problems in particular in urban
centres. It is obvious that the effect will further extend to rural areas as well. Besides, the loss ofeconomic benefits that could have been derived from this sector, cannot survive a growingchallenge of environmentally sound competitive business unless appropriate environmentalmanagement system is introduced.
1.7. It is therefore essential to change this situation by introducing a system that helps improve theenvironmental performance and consequently the productivity of our tanneries. The objectives ofthis guideline are therefore:
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compliance of the standards. The policy further stipulates for the promotion of waste minimizationprocesses, including the efficient recycling of materials.
Other policiesThe Health (Sep.1993) and Water Resources policies have also required prevention of wastes, propermanagement, and protection of aquatic bodies from pollution. Effort should be exerted to closely studythese and other policies in the course of assessment, design and implementation of tannerydevelopment.
3 Tanning Process
3.1 What is Tanning?
Tanning is a process of converting putrescible animal hides and skins to a stable commercial productcalled Leather. Before the tanning process, curd hides and skins arriving at a tannery are trimmed toremove long shanks and unwanted materials for leather making. Then the soaking, liming, fleshing, de-liming, bating degreasing and pickling processes are carried out to create a conductive situation fortanning process.
3.2 Major operations
The production processes in a tannery can be split into four main categories.
3.2.1 Hide and skin storage and beam house operationsHides are prepared for tanning by cleaning and conditioning and by ensuring the correctmoisture. The following processes are typically carried out in the beam house of a tannery.
a) Soaking
The main purpose of soaking is to re-hydrate the hides/ skins ready for subsequent processing, and toremove the salt.
Soaking may be carried out in pit, paddle or drum (or a combination of these) or re-hydrate
the skin and reverse the cure process. Dirt, blood and dung of may also be removed. Chemicals that can be used for this process include sodium-hypochlorite and /or wetting
agent, emulsifiers, surfactants and enzyme preparations.
b) Liming and unhearing This stages removes:-
Hair and epidermis, and further reduces the content of non-collagenous proteins,
A significant proportion of organic pollution is derived from the degraded keratin comprising the hair andepidermis.
Lime blended with sodium Sulphide as traditionally used to loosen wool and hair or dissolved these intopulp. The duration of the process may vary from 18 hours (drums) 7 days (pit). This process isresponsible for the major part of COD Load form tannery. Chemicals include calcium hydroxide (2-10%),(lime), sodium sulphide (1-4%), sodium and sulphydriate, caustic soda, Dimenthylamine sulphate is tootoxic to be recommended.
c) Fleshing and/or splitting
The flesh side of hides /skins still can have excess fat, flesh and connective tissue attached, which mustbe removed prior to further processing .The hides/skins are individually fed through a fleshing machineconsisting of a set of revolving cylinders designated to cut and scrape away the unwanted material .As
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the fleshed hides exit the rear of the machine, some of the rough edges are cut off, producing furtherwaste in the form limed trimmings. (See UNEP-guide Page 17)
3.2.2 Tan yard processTypically, the following processes are carried out in the Tanyard:-
a) Deliming and BatingThe lime in the pelts is no longer required and must be removed to avoid interference with subsequent
tanning and stage, which occurs in acide solution such process is called Deliming. Deliming usingammonium salts carries out-reduction in the pH of the pelts first. Bathing is performed in the same delimefloat and uses enzymes to break down the unwanted protein.
b) PicklingAfter bating, pelts are pre-treated by pickling in salt and Sulphuric acid to prevent precipitation ofchrome salts prior to their addition.
c) TanningTanning processes mainly used for hides or sheep/goat skins include:
- Chrome TanningThe majority of leathers today are chrome tanned in drums from 4 to 24 hours.
chemicals include: 8-12% pelt weight of chrome tanning salt, and as little as 5-6% for low chromeprocesses (basic tri-valiant chromium sulphate hydrated complexes) (22-25% Cr 2O3 ) I.0% sodiumbicarbonate (basifying agent to adjust pH), o.I-o.5% masking agent-sodium formate, phthalate or salts ofdicarboxylic acids, o.I fungicide if product is to be stored/transported in wet blue condition.
- Vegetable TanningWhile vegetable tannage has been eclipsed by chromium as the major tanning process, it is stillemployed for sole saddlery and some specialty leathers. It may also be used as part of a combinationprocess. duration of the process is from I day (drum) to 6 weeks (pit).
Substances used are typically 15-30% of commercial tanning extract (bark or wood of tree, aqueouslyextracted), often sulphitated, then spray dried or concentrated.
3.2.3 Post-tanning Wet WorkThis involves further processing of the stabilized collagen network and may comprise a further tannage(e.g. with combinations of chrome, vegetable, glutaraldehyde or syntan agent) when specialcharacteristics such as perspiration resistance are required. Conditioning softening, dyeing or bleachingmay also be carried out.
Few solid wastes are produced, and the aqueous effluents do not generally contribute significantly to theoverall load of pollutants from the tannery.
3.2.4 Drying and FinishingThe leathers are sammied to remove moisture, and then dried. The final finishing process includes
mechanical treatment of grain and flesh, followed by application of surface finish.The surface coatings consist of dyes or pigments dispersed in a binder, typically casein or an acrylic orpolyurethane polymer, and are applied by padding, spraying or rolling. Nitrocellulose lacquer or urethanelacquer may be applied with organic solvents as top coats. Non-solvent based finishing process arerapidly increasing in use, either through the substitution of aqueous solvents or elimination use ofBenzedine dyes, if still occur rings, should be discontinued due to the toxicity of these substances. .
The major environmental problem in finishing is undoubtedly air emission of solvents. Some aqueouswaters may be generated. Solid wastes may arise from trimmings and buffing dust.
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Finishing
Wetblue:
Chromium tanned hides are often retanned - during which process the desirable properties of more thanone tanning agent are combined and treated with dye and fat to obtain the proper filling, smoothness andcolour. Before actual drying is allowed to take place, the surplus water is removed to make the hidessuitable for splitting and shaving. Splitting and shaving is done to obtain the desired thickness of the hide.The most common way of drying is vacuum drying. Cooling water used in this process is usuallycirculated and is not contaminated.
Crust:
The crust that results after retanning and drying, is subjected to a number of finishing operations. Thepurpose of these operations is to make the hide softer and to mask small mistakes. The hide is treatedwith an organic solvent or water based dye and varnish. The finished end product has between 66 and85 weight percent of dry matter.
A more detailed description of the tanning process is found in the publication Animal by-product
processing by Ockerman and Hansen, 1988.
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Figure 1 schematic of tanning process, indicating waste stream.---
Water Polluants Air polluantsSolid wastes
BOD, COD, SS,DS, salts, Organic N
Green flashings (fatContaining organic matter)
BOD, COD, SSDS, alkalinity H2SSulphides, Organic N Hair, lime, and organicammonia N matter containing sludge
Lime fleshings (fat containingBOD, COD, SS, Ds,limed organic matter)alkalinity
Lime split and trimmings(limed organic matter)
BOD, COD, DS,ammonia N NH3
BOD, COD, DS,fat
BOD, COD, SS,DS, acidity, saltschrome, vegetabletans, syntans,salts Chrome split (chrome-containing
organic matter)
Shavings (chrome-containing
organic matter)BOD, COD, DSchrome, vegetabletans, syntans,dyes, fats
Chrome trimmings (chrome andPrefinishing chemicals containing
Remainder Organic matter)of finishing Solvents, formaldehyde
agents .
RawHide
Soakin
Green Fleshing
Unhearing, Liming
Lime fleshing
Lime splittingTrimming
Finishing
BattingTrimming
Drying
RetanningDyeing
Fat liquoring
Shaving
Chromesplitting
PickilingTanning
Degreasing,(Sheep-pigskins)
Deliming, Bating
Leather
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3.3 Impacts of Tanning Industry on the EnvironmentThere are some positive and negative impacts from the tanning industry.
Positive impact:- Generation of employment opportunity: Economic gain through export market and Local market opportunity from the sell of hides and skins
Negative impact:-The main sources off negative impacts are chemicals used for tanning processes .The tanning industrygives rise to two types of hazard involving chemicals. These are, firstly, those concerning particularchemicals used in the various tanning processes, and secondly, chemical substances produced as by-products by the chemical reactions occurring when a hide undergoes the tanning process.
The first type of hazard includes the vast majority of chemicals to be found in tanning. It ispossible to divide these materials into groups based either on the particular degree of hazardthey present, or on their chemical nature (e.g. acids, alkalis, etc.).
A chemical hazard to workers e.g hydrogen supplied
In terms of toxicity and potential to cause a hazard it is a relatively straight forward task to divide a typicallist of chemicals used in tanning into three groups representing major, moderate, and minor potentialhazards. See annex 1
Also tanning produces hazardous chemical by-products which can be categorized into three generalareas . See annex 2
Tanning and its associated operation while using the different chemicals pointed out in the previousparagraphs can be source of considerable negative environmental impacts. The impacts include-:
Air , water and land pollution, Human health and occupational safety, Loss of economic benefits Damages the ecological processes
3.3.1 Impact on Air, Water and LandTanning generated wastes can cause environmental pollution in different environmental mediums. The
following table presents some pollutants that would cause negative impacts on air, water and land.
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Table 1 POLLUTANTS AND ITS NEGATIVE EFFECT
Pollutants Symbol Main Negative Effects Impact mediumAmmonia NH 3 Pungent odour and adverse effects on aquatic life like fish Water& AirTotal KjeldahlNitrogen TKN
Causes excessive plant growth and formulation of algaecause eutrophication and reduction of oxygen
Water
TrivalentChrome CR III
Toxic to human, aquatic life and crops
At high temperature oxidizes to chrome VI, which is highlytoxic
Water & Land
Chloride Cl Harmful to plants and agriculture, corrodes metal andpiping in civil constructionWater & Land
BiochemicalOxygenDemand(Winkler)
BOD5 BODs indicates the quantity of oxygen may be consumedwhile biologically degrading the organic constitute.
Water
ChemicalOxygen demand(Dichromate)
COD CODs- is measure of oxygen consumed during chemicaloxidation of the constituents of effluents.
Water
Total DissolvedSolids,Sulphates &Chlorides
TDSCL-SO 4
Harmful to plants and civil structuresUnfit for human, industrial and agricultural use
High salinity cause osmotic pressure (reduced wateravailability and retarded plant growthHigh concentrations of sodium ions in irrigation wateraffect the soil structure and properties by causingdispersion of clay
Water & Land
Oil & Grease O&GForms surface films on water and shoreline deposits whichlead to environmental degradation and interfere withbiological processes
Water & Land
PH PHAcidic conditions cause concreter and metal corrosion andare toxic to aquatic lifeHigh alkaline conditions are toxic
Water & Land
SuspendedSolids
SuspendedSolids
Can form deposits and create anaerobic condition (odour)which pose a danger to aquatic life
Water
Sulphide S 2
Odour nuisance at low levels and fatal in highconcentrationsPoisonous to aquatic life, depletes dissolved oxygendamages sewerage systems
Water & Air
SulphateSO 4 May cause corrosion of concrete and piping and limits the
use of the water bodies for both human and agricultureIn anaerobic conditions, can be converted sulphides.
Water & Land
Note: One tone of raw hide converted into about 200 kgs of finished leather the remaining 800 kgs iswaste or pollution.
3.3.2 Impact on human health and occupational safety due to exposure to hazardous chemical The impact of exposure to hazardous material and waste, which emanates from tanning
process include: such as: dizziness, headache, Irritation eyes, skins Allergic Collapse due to lack of oxygen Bronchitis In some rare case even cause death
Hazards related to tannery workers
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The leather industry and in particular tanning processes are notorious for their deleterious environmentalimpacts and occupational health hazards. Working at tanneries involve a series of hazardous processesis presented in Table-2.
Table-2 Hazards related to tannery workers
Physical Hazards Exposure to high noise levels from mechanical equipment.
Callosities on hands caused by continuous work with hand tools
Eye stain due to poor illumination in the tannery.
Chemical Hazards Skin rashes and dermatoses as a result of exposure to cleaners,solvents, disinfectants, pesticides, leather-processing chemicalsetc.
Allergies-contact and systemic-caused by many of the chemicalsused in tanneries.
Biological hazards Raw hides and skins may be contaminated with a variety ofbacteria, molds, yeasts, etc and various diseases (e.g., anthrax,leptospirosis, tetanus, Q-fever, brucellosis, etc.) also the largequantities of dust produced in buffing operations would normallybe contaminated with disease-bearing microorganisms, etc.
Ergonomic,psychosocial andorganizationalfactors
Acute musculoskeletal injuries caused by physical overexertionand awkward posture while moving heavy or bulky loads, inparticular bundles of hides, skins and leather.
Low back pain due to prolonged working in a standing or semi-bending posture
Heat stress, in particular when working on warm days in premiseslacking good ventilation or air conditioning.
Accident hazards Slippery floors, while moving heavy loads such as containers ofchemicals, bundles or hides, skin, leather, etc.
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Electric shocks caused by contact with defective electricmachinery
Blows and crushing injuries caused by rotating or moving parts ofmachinery
Acute poising and/or chemical burns by inhalation, ingestion orskin contact with constituents of tanning process liquors, orpoisonous gases released during the tanning process (e.g.,hydrogen sulfide)
Burns caused by contact with hot surfaces or splashed of hotsolutions
Cuts and stabs caused by manual or mechanized working tools
Eye injuries caused by flying particles from rotary buffingmachines
Asphyxiation or poising in confined spaces, in particular during thecleaning of vats or tanning baths
The employer or the tannery manager is responsible for his workers safety. The employer has theobligation to communicate potential hazard information to the workers in such a way that they canunderstand and are able to avoid the hazards in question. The employer also has the obligation toprovide safety equipments to works so that they can be protected from the likely impact in the tanningprocess.
It is necessary that all workers in the tanning operation have adequate awareness and knowledge aboutthe different kinds of chemicals, their hazardous status etc. One-way of providing a safety andprecautionary measures is to use the most common labels for chemicals in a tannery. These are:
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Fig. 2 Categories of Dangerous Chemicals
The classification is normally presented in the form of an abbreviation representing the category ofdanger together with the appropriate risk phrase or phrases. However, in some cases (i.e. substancesclassified as flammable, sensitizing and some substances classified as dangerous for the environment)the risk phrase alone is used. The abbreviation for each of the categories of danger is shown below:Explosive:
Oxidizing: O Extremely flammable: F+ Highly flammable: F Flammable: R 10 (without symbol) Very toxic: T+ Toxic: T Harmful: Xn Corrosive: C Irritant: Xi Dangerous for the Environment: N
Prevention of chemical hazards to workers
To handle these hazardous chemicals it is necessary to have / to follow the following procedures:-
Material safety data sheets Labels on chemicals containers that show chemical danger
Store chemical safely
Material Safety Data Sheets (MSDS)MSDS are designed to communicate hazard information to the user and public and avoiding any risk tothe worker and the environment. EU Commission Directive 93/112/EC of 10 December 1993 defines andlays down detailed arrangements for the system of specific information relating to dangerous substances.The MSDS is divided into 16 sections as follows:
Chemical product & company information Composition/information on ingredients Hazards identification
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First aid measures Fire fighting measures Accidental release measures Handling and storage Exposure controls/personal protection Physical and chemical properties Stability and reactivity Toxicological information
Ecological information Disposal considerations Transport information Regulatory information Other information like transport requirements
The information in the MSDS is the summary of facts from many sources
Labelling procedure
Labels should specifically indicates:
Trade or brand Name,
Ingredient statement,
Common or chemical name, Type of formulation,
Net content of the package,
Name and address of manufacturer, distributor,
Registration or license number,
Warning or signal words,
Hazards to humans and domestic animals,
Environmental hazards,
Physical and chemical hazards,
Statement of practical first aid treatment,
Re-entry statement,
Storage and disposal directions,
Warranty statement,
Note must be attached to or printed on the side of the container in both English and the official local
languages
Store chemical safely Ensure proper lay out of chemical store,
Fire extinguishers should be placed outside store, Smoking and use of open fire is prohibited,
Shower should be available in or near chemical store,
The following basic rules and principles should be used to store chemical safely
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Storage requirements
All chemical storage areas must be securely fenced to prevent unauthorized access,
All doors and gates should be efficiently locked or padlocked,
In case of fire, the address of the person(s) holding the keys should be fixed to the gate
or door, etc. The building:
Should be constructed of fire-resistant materials such as concrete block or metal,
Should be well ventilated preferably by natural wind flow to minimize temperature
increases and keep fumes from accumulating,
Should be surrounded by a ditch to keep any liquid spills from draining away,
Should be constructed to allow tight security. (Locking doors, barred windows),
Should be well lit by sunlight or electric lights,
Have a water supply for spill decontamination, etc.
Managing chemical stores: First in first out procedure should be followed to minimize the deterioration of
chemicals and containers,
Different types of chemicals should be stored separately to prevent possible cross-
contamination.,
No food, drink or animal feed should be stored in chemical store,
Protective clothing should not be stored in the same room with chemicals
All chemicals should be labelled, etc.
Health and Safety MeasuresAfter understanding the label directions, make certain you have taken the following precautions:
Have detergent or soap and an adequate supply of water available,
Know the early symptoms of poisoning for the chemicals you are using,
Know the first aid procedures and make certain that materials and supplies are available,
Be certain that materials are available to handle spills,
Make certain that all equipment is functioning properly,
Do not work alone; be sure help is available if you get into trouble,
Have all the recommended protective clothing and equipment.
Double-check that the respirator fits properly and has the correct canister cartridge,
Never eat, drink, smoke, or go the bathroom while working with chemicals without first
washing your hands,
Improve working environment
During the production of leather the process on machines and the
chemicals reactions involve emission of heat, dust, gases vapors, noise
vibration to which workers are exposed daily. It is therefore necessary
to:
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Control temperature and humidity through natural and artificial ventilation.
Insulate against heat and cold
Ensure quality of light
Reduces the overall noise level
Personal protective equipment
The most commonly needed personal protective equipment in tanneries and effluent
treatment plants are ;-
Protective clothing (gloves, safety shoes/boots ,aprons)
Hearing protection
Protective goggles and shields and
Respirators
DisposalProducts that cannot be used for their intended purpose (s) or permitted alternatives, and that cannot be
reformulated to become useable again, should be considered for disposal.
The basic procedure for the disposal are the following;-
Remove empty chemical containers from the store and work areas. Dont pour or mix different waste chemicals in the same waste container or barrel Disposal should be made based on study, in approved place and acceptable conditions.
4 THE NEED FOR POLLUTION CONTROLDefining Pollution Prevention
Pollution prevention (P2) is the reduction or elimination of wastes and pollutants at their sources. For allthe pollution that is avoided in the first place, there is that much less pollution to manage, treats, disposesof, or cleanup. P2 can encompass activities such as:
redesigning products to cause less waste or pollution during manufacture, use, or disposal altering production processes to minimize the use of toxic chemicals implementing better housekeeping practices to minimize leaks and fugitive releases from
manufacturing processes taking steps to reduce energy consumption
4.1 Basic waste management hierarchyIn order to minimize the negative impacts emanates from tanning industry ,fundamental pollution controlpractices have to be implemented .The generally accepted waste management hierarchy include
waste:- Prevention and Reduction Recycling and Reuse Treatment and Disposal
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Fig 3- Pollution Prevention HIERARCHY
One of the main principles mentioned in our Environmental policy is pollution prevention.The main reasons for exercising pollution prevention are to:
Protect the environment; Safeguard human health; Create sustainable development and economic benefits of the tanning industry. Normalize the opposition of peoples who are living nearby against the released waste. To produce ecologically sounding product and to get acceptance in the market. For the ease of certification of environmental management system.
Waste reduction at source Exampleo Timely repair/sealing of water and steam leakages from pipes, valves, flanges, etc
- keep taps close when not in use- control of leakages and spillages in the handling and preparation of chemicals and
additives- Avoid Spillage- segregate the line of alkaline from acidic- Reduce material handling losses,- proper maintenance and operations of equipment- By changing process
Recycling, Reuse, Recovery and uses of unnecessary discharges water stream Recovery and reuse onsite
Example:o Recycle back used water.o Lime sulphide recovery from waste sulphide liquor.o Chrome recovery from waste tanning liquor.o condensate recovery and reuse in boiler houses
Creation useful by productsExample:
o manufacturing of glue from lime trimmingso Manufacturing of leather board from shaving dusts.o Conversion of splits to high valuable product etc.
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By changing in put raw materialExample:
o Using fresh hides and skin than salted hides and skins to avoid salt forpreservations etc.
o use non-toxic materialso equipment modificationso install efficient equipment
Technology changeExample:o CO 2 delimingo using short float for the reduction of water consumptiono improve chemical uptake by the leathero use alternative technology for waste minimizationo avoidance toxic and Hazardous Chemicalso Using of water base degreaser, liquor etc.
Fig 4. Pollutant and their management flow chart
By product modificationExample
o production of chrome free leathero produce ecologically sustainable leather
In addition to those mentioned above the following are to be considered. See annex 3
Treatment
GENERAL PRINCIPLES
Some basic data must be investigated and defined for designing and ETP.
o Tannery production and capacity:
- Raw material, processing system (with particular attention to the unhearing and tanningphases), and final product.
- Quantity of the processed material (present and future) as kg or number of hides or skinsprocessed pre day.
- Eventual (possible) internal recycles or recovery.- Water consumption.
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o Factory location:
- Industrial rural or residential zone.- Area available for the ETP.
o Discharge standards
- Limits to discharge, or (in absence) type of recipient and its characteristics (e.g., surface
waters or sewer). In the future the current limits could be subject to change formagnitude or new parameters under control. Therefore the plant must be flexible andexpandable for complying with new stricter impositions. To respect this condition is notalways easy, but, as a principle, extra space for future extension should be considered inthe ETP layout.
o Some common errors done in the project data collection and ETP design are:-
- Incorrect estimate of the water consumption
The water consumption expressed in L/kg of raw material (green or wet salted weight) should notdiffer too much from the following values:
Raw material water consumption (*)Hides (chrome tanning) 25-40Hides(vegetable tanning) 20-30Skins (mixed tanning) 30-60Skins (fur) 50-100
Criteria for selecting the effluent treatment
The tannery effluents are characterized by:-o Intermittent flow,o Wide fluctuation in pH (from 3 to 12)o Big variations in the type and load of pollution (both organic and inorganic).
For achieving the common standards for the discharge into surface waters tannery effluents mustundergo a two steps treatment: primary and secondary. By the term primary those physical chemicaltreatment are meant which precede the biological (secondary) treatment. Only in case of discharge intomunicipal sewer sometimes the installation of the primary treatment alone may be sufficient.
The primary treatment has the following main aims:
o Eliminate the coarse materials as well as abrasives (sand) that can cause clogging ordamage to the pipes and pumps;
o Transform the tannery wastes (which are extremely variable in quantity and quality) into auniform effluent that can be treated in a constant /uniform manner;
o Neutralize too high or low pH values, and eliminate potentially toxic substances (especiallysulphide) that may affect the proper functioning of the biological treatment;
o Reduce the organic load (BOD and COD) and eliminate most of the inorganic suspended
solids in order to reduce the treatment costs and simplify the biological process. Treatment options
The choice therefore is on a technical nature but costs are also involved: on the one hand the primarytreatment must guarantee an effluent suitable for secondary one, on the other the same secondarytreatment may be designed for greater or lesser efficiency. High efficient primary treatments greatlyincrease the volume of generated sludge and associated disposal costs. For this reason the presenttrend is to simplify to the maximum the primary phase, confiding in the secondary one for the maintreatment of the tannery effluent.
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ANNEXES
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Annex 1
CHEMICALS USED IN TANNING PROCESSES(Annex 1)
High Potential Hazard GroupUnder this heading the following chemicals can be listed:
acetic acid hydrogen peroxide
ammonia oxalic acid (slaked lime, lime) sodium chlorite calcium hydroxide sodium hydroxide (caustic soda) formaldehyde sulphuric acid formic acid sulphides and hydrosulphides glutaraldehyde hydrochloric acid (e.g. sodium sulphide, sodium (muriatic acid, spirits of salts) hydrosulphide, calcium hydrosulphide)
Moderate Potential Hazard GroupThe chemicals listed under this heading include:
aluminium sulphate amyl acetate (as lacquer constituents) amyl alcohol (as lacquer constituents) benzyl alcohol (lacquer solvent) carbon black
chromium salts (trivalent) enzymes isopropyl alcohol perchloroethylene toluene white spirit
Low Potential Hazard GroupA third hazard category includes those or negligible hazards:
alums oils acetone paraffin albumen pigment dispersions ammonium chloride sequestering agents ammonium sulphate silicones borax, boric acid sodium acetate casein sodium bicarbonate calcium chloride sodium citrate castor oil china clay sodium carbonate ethanol (ethyl alcohol) sodium formate fat liquors sodium metabisulphite fats sodium nitrite ferrous acetate sodium phthalate ferrous sulphate sodium sulphite gelatine sodium thiosulphate glues (for some glues, solvent synthetic tannins may contribute to toxicity) tragacanth lactic acid titanium salts lanoline vegetable tanning extracts lecithin waxes wetting agents
Miscellaneous Hazards Group Because of wide variations in potential toxic hazard it is not possible tocategorise dyestuffs or fungicides into any one hazard group.
DyestuffsThese may vary widely in toxicity from potentially quite serious if inhaled oringested, to non-toxic.
FungicidesTanneries use several biologically active chemicals to control the growth of various forms of fungal life onthe leather (e.g. TriNap 40). These should all be handled with caution to prevent contact with the skin,inhalation or ingestion by workers
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Annex 2
HAZARDS RESULTING FROM BY-PRODUCTS OF TANNING PROCESSES
Gaseous emissions within the tannery - during processing; the most important in-plantpollutant is hydrogen sulphide, and ammonia may also present problems. Effluent outside the Tannery - The other two areas are those of liquid and solid effluent which
are removed by normal drainage systems, and the release of gaseous wastes into theatmosphere. Each of these results in a problem outside the confines of the factory itself and interms of legislative responsibility the onus rests with agencies other than the Department ofLabour, which under the Factories Act can deal directly only with in-plant problems. TheDepartment of Health has the legislative responsibility for dealing with solid and gaseousenvironmental pollutants such as those arising from tanning processes, while the variousRegional Water Boards have authority over liquid waste discharge.
Generation of Hydrogen Sulphide in Effluent Streams A major hazard which could arise from improperly handled tanning effluent is the generation ofhighly toxic hydrogen sulphide gas. If acidic liquid effluent is not neutralised before being
admitted into the general effluent sewer then its reaction with added sulphide solutions willgenerate hydrogen sulphide Effluent treatment and disposal systems must be designed so as toensure neutralisation of acids before disposal to the general sewer
Annex 3:
Cleaner Production (CP) issues through Tanning ProcessCleaner Production Issues to Consider:
Process fresh hides or skins to reduce the quantity of salt in wastewater, where feasible.
Reduce the quantities of salt used for preservation. When salted skins are used as rawmaterial, preterit the skins with salt elimination methods.
Use salt or chilling methods to preserve hides, instead of persistent insecticides andfungicides.
When antiseptics or biocides are necessary, avoid toxic and less degradable ones,especially those containing arsenic, mercury, lindane, or pentachlorophenol or otherchlorinated substances.
Flesh green hides instead of limed hides.
Use sulphide and lime as a 2050% solution to reduce sulphide levels in wastewater.
Split limed hides to reduce the amount of chrome needed for tanning.
Consider the use of carbon dioxide in deliming to reduce ammonia in wastewater.
Use only trivalent chrome when required for tanning. Inject tanning solution in the skin using high-pressure nozzles; recover chrome from
chrome-containing wastewaters, which should be kept segregated from other wastewaters.
Recycle chrome after precipitation and acidification. Improve fixation of chrome by additionof dicarboxylic acids.
Recycle spent chrome liquor to the tanning process or to the pickling vat.
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Examine alternatives to chrome in tanning, such as titanium, aluminium, iron, zirconium,and vegetable tanning agents.
Use nonorganic solvents for dyeing and finishing.
Recover hair by using hair-saving methods to reduce pollution loads. For example, avoiddissolving hair in chemicals by making a proper choice of chemicals and using screens toremove hair from wastewater.
Use photocell-assisted paint-spraying techniques to avoid over-spraying. Precondition hides before vegetable tanning. Through good management, water use can
be reduced by 3050%, to 25 litres per kilograms (l/kg) of raw material. Recommendationsfor reducing water consumption include the following:
Monitor and control process waters; reductions of up to 50% can be achieved.
Use batch washing instead of continuous washing, for reductions of up to 50%.
Use low-float methods (for example, use 4080% floats). Recycle liming, pickling, andtanning floats. Recycle sulphide in spent liming liquor after screening to reduce sulphidelosses (by, say, 2050%) and lime loss (by about 4060%).
Use drums instead of pits for immersion of hides.
Reuse wastewaters for washingfor example, by recycling lime wash water to the soakingstage. Reuse treated wastewaters in the process to the extent feasible (for example, insoaking and pickling).
Waste reduction measures should include the following:
Recover hide trimmings for use in the manufacture of glue, gelatin, and similar products. Recover grease for rendering. Use aqueous degreasing methods. Recycle wastes to the extent feasible in the manufacture of fertilizer, animal feed, and
tallow, provided the quality of these products is not compromised.
Use tanned shavings in leather board manufacture. Control odour problems by good housekeeping methods such as minimal storage of fleshtrimmings and organic material.
Recover energy from the drying process to heat process water
Annex 4: Tanning Sector (case study on tannery CP ELICO Awash Tannery November 12, 2002
1) Reduction of painting Chemical Consumption
Problem- High chemical consumption168g/lit Na 2S52g/lit NaHS- High BOD level.- Low efficiency of sulphide oxidation in effluent treatment plant.Action Taken- Concentration of chemical reduced. Na 2S from 168g/lit to 135g/lit. NaHS from 52g /lit to 40g/lit.Result of the ChangeNo change in qualityclean sheepskins, no fine hair & no rough skin
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Process 1.8 sheepskins (year).Previous Current annual
consumption kg/annumdifference
in kg/annumNa 2S 100,800 81,000 19,800NaHS 31,200 24,000 7,200Total 132,000 105,000 27,000
Financial Benefit
Total saving of Birr 201,423.96 Birr, asNa2S- Birr 143,324.28NaHS- Birr 58,099.68
Environmental Benefit
- The discharge load has reduced by 27 ton per annum, in terms of total suspended solids (TSS) andalkalinity reduced the volume of water to the effluent treatment plant. More over the new revised processhas shown marked improvement with respect to quality
2) Reduction of Lime Consumption in Hide Liming Process
Problem: - Drawn grain problem.- Excess chemical consumption as
Undissolved lime in the drum.- Long processing time.
Action TakenSoaking time for dry hide reduced from 48 hours to 24 hrs.
Has been reduced.
From 7% to 4% for dry hide.From 3% to 2% for wet salted hide.
From 2.75% to 2% for fresh hide.
Result of the change:
Several tests and assessment on quality show much better result on drawn grain, loose grain & flatness.Touch of the pelt after soaking,Splitting was much better
Total soaked weight inkg/annum,
Previously consumedlime kg/annum
currently consumedlime kg/annum
Dry hide 888,052 62164.0 35522.1Wet salted 69,279 2078.4 1385.6Fresh hide 381,684 10,495.3 7633.7Total limepowderconsumption
74,495.3 44541.4
Financial Benefit- birr 16,668.90 was saved- Unquantified production reduction due to
Productivity improvementquality improvementreduced effluent treatment cost.
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Environmental BenefitReduced the environmental load of lime by 30 ton per annum, in terms oftotal suspended solid (TSS)Alkalinity
3) Chrome Recovery & Reuse
Recovered Chrome inlit/month %Cr 2O3 Amount of 21 % Cr 2O3 (kg/month)1920 12.14 1109.92000 7.3 695.22000 7.0 666.7Total in quarter 2471.8
Financial BenefitAnnual saving Birr 61,392 per annumEnvironmental BenefitReduced chrome load to the environment by 9887 kg per annum.
Financial Benefit
Remedial Step Taken Savings- reducing the size of the
boiler- feeding water tank and
heating it.
409.40Birr/day
- recovering condensate upto 70 0c 32
20.02
- installing more directsteam lines
Birr/day
considering 330 working day & 16 hrs a day annual saving:- Birr162,241.20
4. Collection and Reuse of Painting Spillage
Observation:-Painting solutionSpillage drained to the waste stream
Measurement:-Spillage 16 to 17% of the supplied solution.
The estimated loss of chemical for annual production of 1 million pieces of skinsAnnual Loss in kg Annual Loss in Birr
Na2S (kg) 5136 40060NaHS 3424 24650Lime 17200 10660Total 15760 75370
For complete collection spillage, minimum requirementInsolate the drainage line for painting solutioncollecting tank
Action Taken- Intermediate spillage collecting tank (before the drainage line)- pallet arrangement to reduce water contamination on the floor
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Data was colleted for months show, the following saving.
chemical Na2S(kg) NaHS Lime TotalSaving in kg 194.4 73.3 307.3 575Saving in Birr 1552.20 527.80 190.50 2270.5
Financial Benefit:-Birr 18340 per annum
Environmental Benefit:- Environmental load due to the Na2S, NaHS and Lime by575 kg in three month or4611 kg in a year.
Annex 5: Tannery Effluent Standard
Table 1.1 Emission Limit Values for Discharges to Water
Constituent Group or Parameter Emission Limit Value (mg/l)Temperature 40 CpH 6 9 pH unitsBOD5 at 20 C >90% Removal or 200 mg/lCOD 500Suspended Solids 50Total Ammonia (as N) 30Total Nitrogen (as N) >80% Removal or 60 mg/lTotal Phosphorus (as P) >80% Removal or 10 mg/lOils, Fats, and Grease 15Mineral Oil (Interceptor) 20Chromium (as total Cr) 2Chromium (as Cr VI) 0.1Chloride (as Cl) 1000Sulphide (as S) 1Phenols 1
Table 1.2 Emission Limit Values for Emissions to Air
Substance Concentration Limit (mg/Nm )Total Particulates 50VOCs (degreasing) 50VOCs (finishing) 75 g/m product producedTotal hydrogen sulphide, sulphides and mercaptans(as S)
5 ppm v/v
Ammonia 40 ppm v/v
Acid vapours (as HCl) 30Properly implemented CP:
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P O S T - T
A N N I N G
O P E R A T I O N S
Retaining, chromefixation andneutralization
To enhance exhaustion of post-tanning treatment agents andfixation of tanning agents in the leather
To reduce the salt content of spent liquorsDyeing To enhance exhaustion of dyestuffsFat liquoring To enhance exhaustion of fat liquorDrying To optimize mechanical dewatering prior to drying where
possibleApplying a surfacecoat
To use roller coating To use curtain coating To use HVLP spray guns To use airless spray guns
Exception for all four above-mentioned techniques:- When very thin finishes are applied, e.g. on aniline and aniline-typeleather
Annex 8: BAT for water management and treatment
Within these areas, BAT is:
G O O D
H O U S E
K E E P I N G
A N D
P R O C E S S
I N T E G R A T E D
M E A S U R E
To improve the matching of water flow to the requirements of the processTo use batch versus running water washesTo modify existing equipment to use short floatsTo use modern equipment for short floatsTo re-use waste water in less critical processesTo recycle or re-use process liquors where possible
E F F L U E N T T R E A T M E N T
To keep sulphide-containing effluent from the beam house separate and athigh pH until the sulphide is removed. The associated emission level aftertreatment is 2 mg S 2- /1 in a random sample in the separate effluent. After thesulphide is removed (on site or in a jointly used dedicated treatment plant) theeffluent can be mixed.
To collect chromium-containing partial effluent (e.g. from tanning andsamming) with a concentration of Cr total>1 g/1 separately and send it forchrome recovery. Chrome recovery can be done on or off site.To use mechanical treatment (on or off site)To use biological treatment (on or off site)To use post-purification sedimentation and sludge handling (on or off site)
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a) describe the core elements of the managementsystem and their reaction:
b) provide direction to related documentationo Checking and corrective action
Monitoring and measurement
The organization shall establish and maintain documented procedures tomonitor and measure, on a regular basis the key characteristics of itsoperations and activities that can have a significant impact on theenvironment.
None conformance and corrective and protective actionThe organization shall establish and maintain procedures for definingresponsibility and authority for handling and investigating non-conformance,taking action to mitigate any impacts caused and for initiating andcompleting corrective and prevention action.
RecordsThe organization shall establish and maintain procedures and for the
identification, maintenance and disposition of environmental records. Environmental management system audit:- The organization shall establish and maintain (a) programme (s) andprocedures for periodic environmental management system audits to becarried out, in order to
a) Determine weather or not the environmentalManagement system
b) Provide information on the results of audits tomanagements
Management review
The organizations top management shall, at intervals that is determine, reviewthe environmental management system, to ensure its continuing suitability,adequacy and effectiveness
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References
1. UNIDO /EPA proceeding of consultation and awareness workshop on the industrialeffluent / emission limits for Ethiopia 17-18 April 20032. Provisional standard for industrial pollution control in Ethiopia April 2003 Addis Abab3. Assessment report for the preparation of standards for industrial pollution control in
Ethiopia April 2003 Addis Ababa4. Federal Democratic Republic of Ethiopia industrial environmental policy and strategy
Addis Ababa( 4-7 December 2001)5. UNEP/UNDO Tanneries and environment a technical guide6. ECPC workshop on cleaner production in tanning industries Dec.12/20027. Proclamation No, 1/1995 of the Constitution of the Federal Democratic republic of
Ethiopia8. Papers presented on technical workshop on good practices for the Ethiopian hides and
skin industry 4-7 December 2001 Addis Ababa
9. Ethiopian Environmental Protection Agency Environmental Auditor training course byaspects international Ltd.10. Ethiopian leather journal Vol.1 Oct-Dec. 200411. Health policy of the transitional government of Ethiopia sep,199312. Ministry of water resources ,Ethiopian water resources management policy13. Seminar on tannery pollution control and effluent treatment on Occupational safety and
health aspects of leather manufacture by Netseha Sequar March 29-3114. Public health proclamation No 200/2000 March 29-3115. Environmental policy of Ethiopia April 2,199716. Aspects International Ltd environmental auditor training course 200217. OSH department of labour chemical handling in the chemical industry reformatted 200418. EU Integrated pollution prevention and control (IPPC reference document on best
available techniques for the tanning of hides and skins may 200119. FEPA BAT Best Available Techniques for the Fellmongering and Tanning Industry
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